Bis(cyanomethylidene aromatic aminoalkylcarbamate) compounds



United States Patent Ofice Patented Mar. 31, 1970 U.S. Cl. 260-465 4 Claims ABSTRACT OF THE DISCLOSURE Compounds having the formula wherein X is a cyano, carbamoyl, carbalkoxy or alkylsulfonyl radical, R and R' are each arylene, R and R' are each hydrogen, alkyl, or aryl, R and R' are each alkylene, and R is alkylene, cycloalkylene, arylene, arylenedialkylene, alkylenediarylene or cyclohexylenedialkylene. The disclosed compounds produce fast yellow shades on hydrophobic textile materials such as polyester fibers.

This invention relates to new compounds useful as dyes. More particularly this invention relates to new methine compounds especially useful as dyes for textile fibers, yarns and fabrics.

In the dyeing and printing of textile materials such as fibers, filaments, woven and nonwoven textiles and similar articles of high molecular weight, substances such as cellulose esters, polyamides, polyesters, acrylics and the like, it is of prime importance that the dyes have high color strength and good fastness, e.g. to bleaching, rubbing, drycleaning, heat, atmospheric fumes, perspiration and washing. The dyes should, especially, have good fastness to light.

The methine compounds of the invention possess such properties and have the following general formula:

wherein X, Y, X and Y represent CN; amide radicals such as CONH CONHCH CONHC H SO NH SO NHCH etc.; carbalkoxy radicals, particularly a lower carbalkoxy radicals, such as COOCH and -COOC H cyanocarbalkoxy radicals, particularly lower cyanocarbalkoxy radicals, such as COOC H,CN; or a sulfonyl radical, such as alkylsulfonyl, e.g. methylsulfonyl; Z and Z represent groups derived from an aromatic amine such as aniline and aniline derivatives including those of a monocyclic carbocyclic aromatic amine, for example, N-methylaniline, N-ethylaniline, 3-methylaniline, 3-chloroaniline etc., and bicyclic amines e.g. substituted and unsubstituted dihydroindoles,

l and hydrogenated benzopines,

preferably wherein the nitrogen moiety is either ortho or para with respect to the point of attachment of the methine grouping; and M represents a bis-urethane derivative for example wherein the urethane groups are connected to each other by at least one of the following; alkylene groups, e.g. methylene, ethylene, neopentylene, 1,4-cyclohexanedimethylene etc.; arylene groupss ie a monocyclic aromatic ring of the benzene series, e.g. phenylene, methylphenylene, dimethylphenylene, chlorophenylene; arylalkylene, e.g. 1,4-benzenedimethylene etc.; the urethane groups preferably being respectively attached to the nitrogen moiety of the aromatic amines Z and Z via an alkylene group, especially by a lower alkylene e.g. methylene, ethylene, propylene etc.

Particularly useful compounds of this invention are those compounds wherein Z, of Formula I represents tetrahydroquinolines,

and M represents These compounds are represented by general Formulas II and HI wherein X is as defined above, R and R' represents monocyclic carbocyclic groups of the benzene series including phenylene and substituted phenylene such as phenylene, alkylphenylene, e.g. o,m-tolylene, alkoxyphenylene, e.g.

o,m-methoxyphenylene, halophenylene, e.g. o,m-chlorophenylene, thiocyanophenylene, e.g. o,m-thiocyanophenylene, alkylthiophenylene, e.g. o,m-methylthiophenylene, benzoxyphenylene, e.g. o,m-benzoxyphenylene.

R R R and R' represent hydrogen or alkyl radicals including unsubstituted alkyl, preferably lower alkyl, i.e. from 1 to 4 carbon atoms, and substituted alkyl such as alkoxyalkyl, e.g. methoxyethyl, cyanoalkyl, e.g. cyanoethyl, cyanoalkoxyalkyl, e.g. beta-cyanoethoxyethyl, acyloxyalkyl, e.g. acetoxyethyl, carboalkoxyalkyl, e.g. carboethoxyethyl, halogenoalkyl, e.g. chloroethyl, hydroxyhalogenoalkyl, e.g. beta-hydroxy-gamma-chloropropyl, alkylsulfonylalkyl, e.g. methylsulfonylethyl,

e.g. CH OCOO CH CH carboxyamidoalkyl, e.g. carboxyamidoethyl; benzyl; phenoxyalkyl, e.g. beta-phenoxyethyl; cyanoalkyl, e.g. beta-cyanoethyl; alkylsulfonamidoalkyl, e.g. methylsulfonamidoethyl; alkylcarbonamidoalkyl, e.g. ethylcarbonamidoethyl; dicarboxamidoalkyl, e.g. beta-dicarboxamidoethyl; etc. or R and R represent a monocyclic carbocyclic aromatic group of the benzene series, e.g. unsubstituted phenyl and substituted phenyl, e.g. alkylphenyl, alkoxyphenyl etc.

R and R';; represent lower alkylene groups i.e. a substituted or unsubstituted straight or branched chain of from 1 to 4 carbon atoms e.g., methylene, ethylene, chloroethylene, etc. R represents at least one of the following: alkylene groups e.g. methylene, ethylene, butylene, cyclohexylene, cyclohexanedimethylene etc.; a monocyclic carbocyclic group of the benzene series as for example, those suggested as suitable for the groups R and R or combination of such groups such as aralkylene groups, and alkarylene groups, e.g.

etc.

Q and Q represent alkylene chains of from 2 to 4 carbon atoms making up the remainder of a fused bicyclic nucleus. Q and Q are preferably saturated and may be substituted by one or more groups e.g. hydroXyl, halogen and alkyl, etc. analagous to the substituents listed for R above. Once again it should be emphasized that the aromatic carbocyclic ring of the fused bicyclic nucleus of Formula III may also be substituted as mentioned above for R of Formula II. The substituents attached to the ring nucleus of Z or to N are not critical and serve primarily as auxochromes to control the color of the methine compound.

The distinctive structure of the methine compounds impart unexpected properties to methine compounds, especially when the methine compounds are used for dyeing textiles. These properties include improved fastness to light and improved afiinity for polyester fibers. Thus, the methine compounds in general can be expected to be superior to similar dyes when tested by methods such as described in the A.A.T.C.C. Technical Manual,

1964 edition, depending in part upon the particular dyeused and the fiber being dyed.

The methine compounds of this invention can be prepared by reacting a bis-isocyanate for example of the formula wherein R is as described above, with an appropriate N (hydroxyalkyl) aniline derivative. The aromatic rings of the aniline moieties of the resultant bis-urethane are then fcrmyl ted ther by o m g i -ureth e-dialdehyde. The aldehydic groups are then reacted with an active hydrogen compound of the general formula XOY wherein X and Y are defined above, to form the methine compounds.

The resultant methine compounds can be used for dyeing textile materials including synthetic polymer fibers, yarns and fabrics giving fast shades of yellow, when applied thereto by conventional dyeing methods. The compounds have moderate affinity for cellulose ester and polyamide fibers and possess the valuable property of staining wool less than do previous methine dyes. When the methine compounds are used for dyeing such hydrophobic materials, they should be free of water-solubilizing groups such as sulfo and carboxyl. In general the dyes have good fastness, for example, to light, washing, gas (atmospheric fumes) and sublimation.

The following examples will serve to illustrate the preparation of representative methine compounds of our invention.

EXAMPLE I (a) Preparation of the bis-urethane.A mixture of 33 g. of N-ethyl-N-beta-hydroxyethylaniline, 17.4 g. t0lylene-2,4-diisocyanate, and ml. benzene was stirred and refluxed for 3 hours. While still hot, the solution was poured into a 250 ml. beaker and allowed to stand overnight at room temperature. The bis-urethane precipitated and was filtered off, washed with benzene, and dried. The yield was 40.9 g. of a white solid, M.P. 9798 C. Analysis for C and H checked Well for the compound of the following structure:

(b) Preparation of the dialdehyde.-13 g. of the product from (a) above was dissolved in 100 ml. dry dimethylformamide. The solution was stirred and cooled in ice and 6 ml. POCl was added dropwise with the reaction temperature l015 C. When the addition was complete, the reaction was heated 2 hours on the steam bath. The reaction mixture Was drowned in 1 liter of water, and it all dissolved, then came back out as a sticky mass. The gummy material solidified after several water washings by decantation. This product was ground under water, filtered, washed with water, and dried at room temperature. It was used directly in the next step without further purification.

(c) Preparation of the dye-All of the product from (b) above, 3.3 g. malononitrile, and 250 ml. ethanol, in the presence of 2 drops piperidine for catalyst, were heated on the steam bath 2 hours. On cooling to room temperature, a glassy precipitate resulted. The alcohol was decanted, and the glass allowed to stand overnight. It was then ground and dried in the air. The yield was 8.4 g. of a yellow dye of outstanding fastness to dry sublimation on polyesters. A sample recrystallized from n-amyl alcohol melts at 102103 C. The dye has the following structure:

The following table shows additional examples of dyes which were prepared according to the general method outlined in Example I. The substituents indicated are with reference to Fo m la I.

The methine compounds of the invention may be used for dyeing hydrophobic fibers such as linear polyester, cellulose ester, acrylic, polyamide, etc., fibers in the manner described in US. Patents 2,880,050, 2,782,187 and 2,043,827. These dyes all render such fibers varying shades of yellow and have excellent light fastness and resistance to sublimation. The following examples illustrate methods by which the methine compounds of the invention can be used to dye polyester textile materials.

0.1 gram of the dye is dissolved in the dye pot by warming in cc. of ethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurate and 0.5% sodium lignin sulfonate aqueous solution is added, with stirring, until a fine emulsion is obtained. Water is then slowly added to a total volume of 200 cc. 3 cc. of Dacronyx (a chlorinated benzene emulsion) are added and grams of a textile fabric made of Kodel polyester fibers are entered. The fabric is worked 10 minutes without heat and then for 10 minutes at C. The dyebath is then brought to the boil and held at the boil for one hour. Following this, the fabric is rinsed in warm water, then scoured in an aqueous 0.2% soap, 0.2% soda ash solution. After scouring, the fabric is rinsed with water and dried. Accordingly, since the methine compounds of the invention are water-insoluble, they can be applied from aqueous dispersions in the manner of the so-called dispersed dyes. However, coloration can also be effected, for example, by incorporating the methine compounds into the spinning dope and spinning the fiber as usual. The methine compounds of our invention have varying utility as dyes. The degree of utility varies, for example, depending upon the material being dyed and the formula of 7 8 the methine compound. Thus, for example, all the dyes R and R' each represents p-phenylene, lower-alkyl-pwill not have the same degree of utility for the same matephenylene, lower alkoxy-p-phenylene, or chloro-prial. phenylene,

By cellulose aliphatic carboxylic acid esters having 2 R and R each represents hydrogen; lower alkyl; to 4 carbon atoms in the acid groups thereof, we mean lower alkyl substituted with methoxy, cyano, 'acetoxy, to include, for example, both partially hydrolyzed and un- U cyanoethoxy, carboethoxy, chlorine, methylsulfonyl, hydrolyzed cellulose acetate, cellulose propionate and cel- CH OCOO, phenoxy or methylsulfonamido; lulose acetatebutyrate. benlyl, of p y Polymeric linear polyester materials of the terephthal- 3 and 's each represents lower a1ky1ene;al1d

R represents alkylene of 1 to 6 carbon atoms, cyclohexylene, phenylene, lower alkylphenylene, lower alkoxyphenylene, chlorophenylene, benzenedimethylene, cyclohexanedimethylene, or diphenylenemethane.

2. A compound according to claim 1 wherein X represents cyano;

R and R; each represents lower alkyl or lower cyanoate type are illustrative of the linear aromatic polyester 10 textile materials that can be dyed with the new methine compounds of our invention. The terephthalate fibers sold under the trademarks Kodel, Dacron and Terylene, for example, in the form of filaments, yarn and fabric, for example, are illustrative of the polyester textile materials that can be dyed. Kodel polyester fibers are more a1ky1.and

particularly described in US. Patent 2,901,446. Dacron R 4 reprsents alkylene of 1 to carbon atoms phenyl and Terylene polyester fibers are described, for example, em, lower .alkylphenylene, cyclohexylene, 6 cyc1o in Us. Patent 2,465,319. The polymeric linear polyester hexanedimethylene materials disclosed in Patents 3 A ompound according to claim 1 having the forand 2,989,363, for example, can be dyed. The linear arol matic polyester materials specifically named have a melt- 4. A compound according to claim 1 having the ing point of at least 200 C. formula:

NO CzHaCN O O C2H4CN CN l H II I /C- H o C2H4OCNH- NH O O C2H4N' 011:0 NC CN H3 CH3 Nylon, in fiber, yarn and fabric form is representative of polyamides which can be dyed with the methine comf rences Cited pq h be d d M d t UNITED STATES PATENTS e inven 1011 as en escri e in 601181 era e e at with particular reference to certain preferred embodi- 10/1956 'Kartmos 6t 260465 X ments thereof, but it will be understood that variations 7/1964 stfaley et a1 260465 X and modifications can be efiected Within the spirit and 3247215 4/1966 Flsher at 260-465 X scope of the invention as described hereinabove. 3386491 6/1968 Weaver at 31 X We claim: Dale et al. -1. A compound having the formula R2 0 0 RE X CHARLES B. PARKER, Primary Examiner 0g g 1 S. T. AsSiStant Examiner NO ON 50 US. 01. X.R. wherein X represents-CN, CONH --CONH-lower-alkyl, 8-54.21, 54, 55, 57, 62, 63; 117--138.8; 2160-239, 287,

'COO-lower-alkyl, COOCH CH CN, or SO 326.12, 326.13, 326.14, 453, 454, 468, 472, 482 lower-alkyl;

Pg/EggO UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3:5 b Dazed March 3 1970 hvflumg) James M. Straley and David J. Wallace It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

olumn 2, lines 62 through 68, formula (III) should read:

X X I C: CH -Q,\ ,Q-- CH C P m N O O QN Column 3, line 33, "R should be -R' Columns 5 and 6, Example 3, in the Table under the heading "Z" he formula should read:

Columns 5 and 6, Example 6, in the Table under the heading "M", the formula should read:

0 0 II II g ggo UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 5,50 1 Dated March 51 1970 Patent No.

Inventor) James M. Straley and David J. Wallace It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Columns 5 and 6, Example 7, under the heading "M" in the Table,

the formula should read:

0 ll g C2H4OCNH NHCO 2H4- Column 8, Claim 5, lines 23 through 29, the formula should read:

NC L N c=Hc -C2H4OCNH CH3 NC/ C2H5 CN NHCOC2H41L CHIC ll cN Column 8, Claim 4, lines 33 through .36, the formula should read:

C2H4CN 0 o C2H4CN NC I l I /CN C=H N-C H OgNH NHGOC2H4-N CH=C\ NC CN CH3 CH3 Signed and sealed this 9th day of February 1971.

(SEAL) Atteat:

EdwardlLFletchmIr. Att WILLIAM E. SOHUYIMR, JR. estmg Officer Commissioner of Fame! 

